| Revision as of 14:44, 13 December 2010 editTruthCollector (talk | contribs)35 edits ethylenediamine is organic material ??← Previous edit |
Latest revision as of 20:13, 6 August 2024 edit undoJWBE (talk | contribs)Extended confirmed users10,126 edits removed Category:Metal halides using HotCat |
| (58 intermediate revisions by 32 users not shown) |
| Line 1: |
Line 1: |
|
{{DISPLAYTITLE:''cis''-Dichlorobis(ethylenediamine)cobalt(III) chloride}} |
|
{{DISPLAYTITLE:''cis''-Dichlorobis(ethylenediamine)cobalt(III) chloride}} |
|
{{chembox |
|
{{Chembox |
|
|
| Verifiedfields = changed |
| ⚫ |
| verifiedrevid = 399718045 |
|
|
|
| Watchedfields = changed |
| ⚫ |
| Name=''cis''-Dichlorobis(ethylenediamine)cobalt(III) chloride |
|
|
⚫ |
| verifiedrevid = 402148878 |
| ⚫ |
| ImageFile = Cis-Dichlorobis(ethylenediamine)cobalt(III) chloride.png |
|
|
| Name = cis-dichlorobis(ethylenediamine)cobalt(III) chloride |
|
| Name = ''cis''-Dichlorobis(ethylenediamine){{SHY}}cobalt(III) chloride |
|
⚫ |
| ImageFile = Cis-Dichlorobis(ethylenediamine)cobalt(III) chloride.png |
| ⚫ |
| OtherNames = |
|
|
|
| ImageSize = 220 |
| ⚫ |
| Section1 = {{Chembox Identifiers |
|
|
⚫ |
| ImageAlt = Skeletal formulas of cis-dichlorobis(ethylenediamine)cobalt(III) chloride |
| ⚫ |
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
|
|
| ImageFile1 = |
|
|
| ImageSize1 = 230 |
|
|
| ImageAlt1 = sample |
|
⚫ |
| OtherNames = |
|
⚫ |
|Section1={{Chembox Identifiers |
|
⚫ |
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| ChemSpiderID = 360279 |
|
| ChemSpiderID = 360279 |
|
| PubChem = 407212 |
|
| PubChem = 166987 |
|
| InChI = 1/2C2H6N2.2ClH.Co/c2*3-1-2-4;;;/h2*3-4H,1-2H2;2*1H;/q2*-2;;;+2/p-2 |
|
| InChI = 1/2C2H6N2.2ClH.Co/c2*3-1-2-4;;;/h2*3-4H,1-2H2;2*1H;/q2*-2;;;+2/p-2 |
|
| InChIKey = LBGRXLRZGLIOLI-NUQVWONBAE |
|
| InChIKey = LBGRXLRZGLIOLI-NUQVWONBAE |
| Line 17: |
Line 23: |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey = LBGRXLRZGLIOLI-UHFFFAOYSA-L |
|
| StdInChIKey = LBGRXLRZGLIOLI-UHFFFAOYSA-L |
|
|
| CASNo_Ref = {{cascite|correct|??}} |
|
| CASNo = 14040-32-5 |
|
| CASNo = 14040-32-5 |
|
| RTECS = |
|
| RTECS = |
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
|Section2={{Chembox Properties |
|
| Formula = C<sub>4</sub>H<sub>16</sub>Cl<sub>3</sub>CoN<sub>4</sub> |
|
| Formula = C<sub>4</sub>H<sub>16</sub>Cl<sub>3</sub>CoN<sub>4</sub> |
|
|
| C=4 | H=16 | Cl=3 | Co=1 | N=4 |
|
| Appearance = violet solid |
|
| Appearance = violet solid |
|
| Density = |
|
|
| Solubility = good |
|
| Density = |
|
|
| Solubility = good |
|
| MeltingPt = dec. |
|
| MeltingPt = decomposes |
|
| BoilingPt = |
|
| BoilingPt = |
|
}} |
|
}} |
|
| Section3 = {{Chembox Structure |
|
|Section3={{Chembox Structure |
|
| Coordination = |
|
| Coordination = |
|
| CrystalStruct = |
|
| CrystalStruct = |
|
}} |
|
}} |
|
| Section7 = {{Chembox Hazards |
|
|Section7={{Chembox Hazards |
|
| ExternalMSDS = |
|
| ExternalSDS = |
|
|
| GHS_ref=<ref>{{cite web |title=575909 |url=https://www.sigmaaldrich.com/AU/en/sds/aldrich/575909 |publisher=sigma |access-date=15 December 2021}}</ref> |
|
| EUClass = |
|
|
| RPhrases = {{R36/37/38}} |
|
| GHSPictograms = {{GHS07}} |
|
|
| GHSSignalWord = Warning |
|
| SPhrases = {{S26}} {{S36}} |
|
|
|
| HPhrases = {{H-phrases|315|319|335}} |
| ⚫ |
| FlashPt = |
|
|
|
| PPhrases = {{P-phrases|P261|P264|P271|P280|P302 + P352|P304 + P340|P305 + P351 + P338|P312|P321|P332 + P313|P337 + P313|P362|P403 + P233|P405|P501}} |
| ⚫ |
}} |
|
|
⚫ |
| FlashPt = |
|
⚫ |
}} |
|
}} |
|
}} |
|
⚫ |
'''''cis''-Dichlorobis(ethylenediamine)cobalt(III) chloride''' is a salt with the formula Cl (en = ]). The salt consists of a cationic ] and a chloride anion. It is a violet diamagnetic solid that is soluble in water. One chloride ion in this salt readily undergoes ], but the two other chlorides are less reactive, being bound to the metal center. |
|
|
|
|
|
⚫ |
==Synthesis and optical resolution== |
| ⚫ |
'''''cis''-Dichlorobis(ethylenediamine)cobalt(III) chloride''' is an ] with formula Cl (en = ]). It is a violet diamagnetic solid that is soluble in water. One chloride ion in this salt readily undergoes ion exchange but the two other chlorides are less reactive, being bound to the metal center. |
|
|
|
''Cis''-dichlorobis(ethylenediamine)cobalt(III) chloride is obtained by heating a solution of ], e.g. using a steam bath. |
|
|
|
|
|
⚫ |
The ] can be ] into two ]s (Λ and Δ) by the formation of the ''d''-α-bromocamphor-π-sulfonate salt. The ]ic salts are separated by recrystallization. After their purification, the individual diastereomers are converted back to the chloride salt by reaction with ice cold hydrochloric acid.<ref>{{cite book|author=John C. Bailar, Jr.|title=''Cis''- and ''Trans''-Dichlorobis-(Ethylenediamine)Cobalt(III) Chloride and the Resolution of the ''Cis'' Form|chapter=Cis - and trans -Dichlorobis-(ethylenediamine)cobalt(III) Chloride and the Resolution of the cis Form |series=Inorganic Syntheses|year=1946|volume=2|pages= 222–225|doi=10.1002/9780470132333.ch71|isbn=9780470132333 }}</ref> |
|
==Synthesis== |
|
|
|
<gallery class="center"> |
|
''Cis''-Dichlorobis(ethylenediamine)cobalt(III) chloride is obtained by heating ''trans''-Cl e.g. using a steam bath. The trans isomer is in turn synthesized by the reaction of ] and ] in hydrochloric acid in the presence of oxygen: |
|
|
:4 CoCl<sub>2</sub> + 8 en + 4 HCl + O<sub>2</sub> → 4 ''trans''-Cl + 2 H<sub>2</sub>O |
|
File:Delta-cis-dichlorobis(ethylenediamine)cobalt(III).png|Λ-''cis''-<sup>+</sup> |
|
⚫ |
File:Lambda-cis-dichlorobis(ethylenediamine)cobalt(III).png|Δ-''cis''-<sup>+</sup> |
|
The initial product contains HCl, which is removed by heating. Alternatively, (carbonato)bis(ethylenediamine)cobalt (III) chloride reacts with hydrochloric acid at 10 °C to give the same species.<ref>Springbørg, J.; Schaffer, C.E. “Dianionobis(Ethylenediamine)Cobalt (III) Complexes” Inorganic Synthesis, 1973; volume 14, pages 63-77. {{DOI|10.1002/9780470132456.ch14}}</ref> |
|
|
:Cl + 2 HCl → ''trans''-Cl + CO<sub>2</sub> + H<sub>2</sub>O |
|
|
|
|
| ⚫ |
==Optical resolution== |
|
| ⚫ |
The cis isomer is formed as a ], which can be ] into two ]s (Λ and Δ) by the formation of the ''d''-α-bromocamphor-π-sulfonate salt. The ]ic salts are separated by recrystallization. After their purification, the individual diastereomers are converted back to the chloride salt by reaction with ice cold hydrochloric acid.<ref>], J.C. “Cis- and Trans-Dichlorobis-(Ethylenediamine) Cobalt (III) Chloride and the Resolution of the Cis Form”. Inorganic Synthesis, 1946, volume 2, pages 222-225. {{DOI|10.1002/9780470132333.ch71}}</ref> |
|
|
<center> |
|
|
<gallery> |
|
|
Image:Delta-cis-dichlorobis(ethylenediamine)cobalt(III).png|<center><sup>+</sup>]]</center> |
|
| ⚫ |
Image:Lambda-cis-dichlorobis(ethylenediamine)cobalt(III).png|<center>Δ-''cis''-<sup>+</sup></center> |
|
|
</gallery> |
|
</gallery> |
|
|
<sup>+</sup> to the cis isomer.]] |
|
</center> |
|
|
|
|
|
|
|
==Related complexes== |
|
==Comparison of cis and trans isomers== |
|
|
This salt is less soluble than the dull-green isomeric ''trans''-Dichlorobis(ethylenediamine)cobalt(III) chloride (CAS#14040-33-6). This pair of isomers were significant in the development of the area of ].<ref>Jörgensen, S.M. “Ueber Metalldiaminverbindungen“ J. prakt. Chem., 1889, volume 39, page 8. {{DOI|10.1002/prac.18890390101}}</ref> The chiral cis isomer can be obtained by heating the trans isomer. Both isomers of dichlorobis(ethylenediamine)cobalt(III) chloride have often used in stereochemical studies and as intermediates (like ]) for the preparation of other cobalt salt complexes. |
|
This salt is less soluble than its dull-green isomer ''trans''-dichlorobis(ethylenediamine)cobalt(III) chloride. This pair of isomers were significant in the development of the area of ].<ref>Jörgensen, S.M. "Ueber Metalldiaminverbindungen" '']'' (in German), 1889, volume 39, page 8. {{doi|10.1002/prac.18890390101}}</ref> The chiral cis isomer is obtained by heating the trans isomer. Both isomers of dichlorobis(ethylenediamine)cobalt(III) have often been used in stereochemical studies. |
|
|
|
|
|
|
] in contrast to the bis(ethylenediamine) complexes does not undergo substitution. |
|
==Properties of the trans isomer== |
|
|
Crystallographic analysis shows that the trans isomer has the following bond distances: Co-N: 1.99, Co-Cl: 2.22, C-N: 1.47, C-C 1.54 Å.<ref>Sharma, R. J.; Sharma, R.; Bala, R; Salas, J. M.; Quiros, M. “Second sphere coordination complexes via hydrogen bonding: Synthesis, spectroscopic characterisation of CdX<sub>4</sub> (X=Br or I) and single crystal X-ray structure determination of CdBr<sub>4</sub>” Journal of Molecular Structure, 2006, volume 794, pages 342-344. {{DOI|10.1016/j.molstruc.2006.02.053}}</ref> The trans isomer cation has idealized D<sub>2h</sub> point group symmetry, whereas the cis isomer cation has C<sub>2</sub> symmetry. |
|
|
|
|
|
|
==References == |
|
== References == |
|
<references/> |
|
<references/> |
|
|
|
|
|
{{DEFAULTSORT:Dichlorobis(ethylenediamine)cobalt(III) chloride, cis}} |
|
{{DEFAULTSORT:Dichlorobis(ethylenediamine)cobalt(III) chloride, cis}} |
|
] |
|
] |
|
|
] |
|
] |
|
] |
|
] |
|
] |
|
] |
|
] |